Stilbene bis triazole azo dyestuffs



Patented Feb. 22, 1949 UNITED STATES PATENT orrlce STILBENE BIS TRIAZOLE AZO DYESTUFFS Ernst Keller and Reinhard Zweidler, Basel, Switzerland, assignors to J. R. Geigy A.-G., Basel, Switzerland, a Swiss firm No Drawing. Application November 27, 1945, Se-

rial No. 631,224. In Switzerland November 24,

10 Claims.

3103B: SIOSH wherein A means a benzene or naphthalene radical with at least one solubilising group, such as a COOH- or SOsH-group, which radical may still further be substituted, and X means hydrogen or an alkyl, alkoxy, sulfonic acid or carboxylic group or halogen.

The stilbene-bis-triazols not known heretofore may advantageously be prepared for instance by coupling 4-nit1'o-4 -diazo-stilbene-2 2 -disulfonic acid with 5-amino 2-aryl-l:3-benztriazols and oxidising the coupling products by means of suitable oxidising agents thus giving the bis-triazols. As oxidising agent may be enumerated for example cupric salts in an alkaline solution, lead peroxide, manganese dioxide, eventually also sodium hypochlorite and the like. The new stilbene-bis-triazols obviously must be formulated as angular bis -triazols. As proved by P. Schmidt and A. Hagenbticker (Berichte der deutschen chemischen Gesellschait 54, 2201) as well as by K. Fries and G. Walnitzki (Annalen der Chemie 511, 267) 5-amino-2-phenyl-1:3-benztriazols N l O N l couple in4-position; thus, when oxidising the azo dyestufi from diazobenzene and 5-amino-2- phenyl-1i3-benztriazol, the bis- (Z-phenyl-l :2 3-

triazolo) -benzene of the following formula is produced:

In view of the foregoing the new stilbene-bistriazols claimed herein certainly correspond to the above formulated general formula having an angular tricyclus'and this particularly, since the same may also be prepared, when the fi-position of the benztriazol is occupied.

Among the great nulnber of stilbene-bis-triazols, which maybe used as condensation compo'nents, the following ones may be enumerated for example only, these compounds being obtainable by coupling 4-nitro-4-diazostilbene-2 2'-disulfonic acid (St) with 5,-amino-2-aryl-1:3-benztriazols andioxidising the azo dyestuff.

SOaH $0311 From St 5-amino-2-(3-carboxypl1enyl)-1:3-bcnztriazol 0 O OH N- From St 5-amino-2-(4-hydroxy-3-carboxy-5'-methylphenyl)-l:3-benztriazol also such ones, which contain the saponifiableacylamino groups and more particularly metallisable groups, may be particularly cited in this connection. Of course, any possibilities and variations known for the manufacture of nitrostilbene condensation products may be applied-for the condensation and after-treatment. may be mentioned for instance the condensation in presence or absence of pressure, the aftertreatment with oxidising agents, with metalyielding agents on the fibre or in substance and on the fibre respectively.

Moreover, there may especially be mentioned that it is possible to after-treat dyeings of metal complex compounds with the same metal or with another metal than that used for the formation of: the complex compound. 7

The dyeings of the new dyestufis onto cellulosefibres'are generally distinguished by good fastness properties in the moist state and by a good to very good light-fastness. Moreover, in such cases, where the dyestufls contain metalli'sable groups, the fastness properties in the moist state can still considerably be increased by an aftertreatment with metal salts and more particularly with salts of copper and chromium.

The following examples, in which the parts are by weight, illustrate the invention without being limitative.

Example 1 40 parts of diazotised 4:4-nitroaminosti1bene- 2:2'-disulfonic acid are coupled with 35 parts of 5-amino 2 (4-hydroxy-3'-carboxyphenyl) -1':3--

benztriazol. The red dyestuff is filtered oif, dissolved in 3000 to 4000 parts of hot water with addition of ammonia and oxidised at 95-98 C. with a solution of 60 parts of crystallised copper sulfate and 120 parts of concentrated ammonia. The copper complex of the bis-triazol is split open by heating the same with hydrochloric acid. After isolation the nitrostilbene-bis-triazol is obtained in form of a yellow substance. 75.9 parts of the so obtained compound and 25.7 parts of 4-amino-4'-hydroxy-1:1'-azobenzene-3'- carboxylic acid are condensed under reflux at boiling temperature for -20 hours with 1600 parts of water and 400 parts of caustic soda lye of 36 B., neutralised with hydrochloric-acid after cooling, precipitated by means of sodium chloride and filtered off. The dried dyestufi is a dark brown powder dissolving in water with a yellow coloration and dyeing cellulosic fibres in yellow shades. The good fastness properties to washing and to water of the dyeings thus produced can still further be improved by an after-treatment with chromium salts.

Thus

A dyestufi having similar properties is obtained by coupling 40 .parts of diazotised 4:4'-nitroaminostilbene-2:2-disulfonic acid with 35 parts of 5 amino-2-(2'-hydroxy-3'-carboxy-5'-sulfophenyl)-1:3-benztriazol and oxidising with copper sulfate and ammonia or lead dioxide in order to produce the nitrostilbene-bis-triazol, the latter being finally condensed in the manner indicated above with 25.7 parts of 4-amino-4'-hvdroxv- '1:1'-azobenzene 3 earboxylic acid.

Example 2 75.9 parts of the stilbene-bis-triazol (Formula 6) described in Example 1 and 32 parts of dehydrothio-p-toluidine-sulfoc 1ic acid are condensed under reflux for 18 hours in 1500 parts of water and 500 parts of caustic soda lye of 36 B. The difiicultlysoluble condensation product is filtered oiT and dried. The dyestufi constitutes a yellow powder dissolving in water with a yellow coloration and dyeing cellulosic fibres in yellow shades of good fastness properties to water, washing and to light. Since the dyestufl leaves wool practically completely white, it is particularly valuable also for thedyeing of half-wool. By an aftertreatment with copper or chromium salts the fastness properties in the moist stateare still improved.

Further similar dyestufis are obtained by replacing the above stilbene-bis-triazol by stilbenebis-triazols of the Formulae 5, 7, 8, 9 or 18.

Example 3 75.9 parts of the stilbene-bis-triazol (Formula 6) disclosed in Example 1 and 42 parts of 2-(4- aminophenyl) -(napht ho -1' :2 :4:5-triazo1) -5' :7 disulfonic acid are condensed for 12 hours at C. in a pressure vessel containing 1000 parts of water and parts of caustic soda lye of 36 B, The condensation product is precipitated by means of sodium chloride, filtered off and dried. The dyestufi is a yellow powder, which dyes cellulosic fibres in yellow shades being distinguished by good fastness properties to washing and to water and by a very good light-fastness. By an after-treatment with chromium or copper salts the fastness properties in the moist state are still improved.

By treating the above dyestufi in an alkaline solution with sodium hypochlorite there will be obtained a product dyeing fibres in still somewhat purer yellow shades.

Further "similar dyestuffs are obtained by substituting the 2 (4 aminophenyl) (naphtho- 1':2':4:5-triazol)-5:7-disulfonic acid by one of the following naphtho-triazol compounds: 2-(4- aminophenyl) (naphtho 1' :2 :4:5 triazol) 4- Example 4 75.9 parts of the stilbene-bis-triazol described in Example 1 (cf. Formula 6) and 25.8 parts of 4' amino 2 methoxy-2-hydroxy-1:1'-azobenzene-5-sulfamide are heated to boiling under reflux for 15-20 hours in 2000 parts of water and 450 parts of caustiosoda lyeof 36 B. and isolated in the usual manner. The dyestufi is a dark brown powder dissolving in-water with a brownred coloration and dyeing cellulosic fibres in brownish-red shades. -By an after-treatment-with copper salts bordeaux-red shades of good fastness properties to washing and to water as well asof a very good light-fastness are produced.

Example When condensing 759 parts of the stilbene-bistriazol made according to Example 1 (Formula 6) with 34.9 parts of the monoazo dyestuff obtainable from diazotised anthranilio acid and 2-amino-5- hydroxvnaphthalene-Fl -sulfonic acid in 2000 parts of water and 500 parts of caustic soda .lye of 36 B., there Will be obtained, after isolation, a brown powder. This dyestui'l dissolves in water with a red coloration and dyescellulosic fibres in redshades. When after-coppered. a brown-red dyeing of good fastness properties to washing and to water as well as of ,a verygoodlight-fastness is obtained.

By treating the dyestuii in substancewith copper salts in a slightly acid medium the metallised Example 6 75.9 parts of the stilbene-bis-triazol disclosed in Example 1 (Formula 6) are condensed in the usual mannerwith 4L6 parts of the azo dyestuff obtainable from l-amino-d-acetyl-aminoor initrobenzene 2 carboxylic acid 1-,(4'-sulfophenyl) -3-methyl-pyrazolone and saponified or reduced by means of sodium sulfide respectively, the condensation being carried out in 1700 parts of water and 300 parts of caustic soda lye of 36 B. Then the product is-lisolated. Thus a yellowbrown powder is obtained which dissolves in water with a yellow coloration. The dyestufi dyes cellulosic fibres in reddish-yellow shades becoming only slightly dull, when after-treated with copper salts, and being distinguished by good fastness properties to washing, water and to light.

The same dyestuff is also obtained by condensing the unsaponified monoazo dyestuff from diazotised l-amino-4-acetylaminobenzene-2-carboxylic acid and 1-(4-sulfophenyl) -3-methylpyrazoione in the above manner withthe stilbenebis-triazol.

Example 7 this nitro compound and 32.9 parts of the mono- 6 azo dyestufi obtainable from diazotised l-aminobenzene-Z-carboxylic acid and Z-amino-S-hydroxy-naphthalene-7-sulfonic acid are condensed under reflux at boiling temperature for 15-20 hours in 1600 parts of water and 400 parts of caustic soda lye of 36 B., the resultingprodnot being isolated in the usual manner. The dyestuff is a brown powder dissolving in water with a reddish-brown coloration and dyeing cellulosic fibres in brown-red shades. The fastof this .nitrostilbene-bis-triazol (Formula 5) with 10 ness properties to light and in the moist state are increased by an after-treatment with copper salts.

Example 8 40 parts of 4:4-nitroaminostilbene-2:2-'-disulionic acid are diazotised and coupled with 42 parts of 5-amino-2: 2- (4 :8-,disulionaphthyl) 1:3-benztriazol. The dyestuii is oxidised with an ammoniacal coppersulfate solution at C. or with sodium hyl Qohlorite at 35-40 C. in a slightly alkaline medium in order to produce the nitrostilbene-bis-triazol (Formula 11). The nitro compound is a canary-yellow powder dissolving in water with a slightly yellow coloration.

80.8 parts of this nitrostilbene-bis-triazol and 37.8 parts of the monoazo .dyostuii obtainable from diazotised 2-aminomaphthalenad:8-disulfonic acid and l-amino-B-methylbensene are condensed :in the usual manner in 1:69 parts of water and 300 parts of caustic'soda lye of 36B.

and isolated. Thus an orange powder is obtained which .dissolves in water with a yelloworange coloration and dyes cellulosic fibres in yellow-orange shades of good fastness properties to washing, water and to light.

Example 9 .40 partsof diazotised 4:4=nitroaminostilbene- 2:2'-disulfonic acid are coupled with 35 parts of 1,5 amino-2-(14-hydroxye3-carboxyphenyl) -.6-

sulfo-lz3-benztriazol and the resulting azo dyestuff is oxidised-in'the usual manner to the nitrostilbene-bis-triazol (Formula 5). The nitroibody is a yellow powder dissolving in Water with a yellow coloration. When condensing 75.9 parts by condensing the nitrostilbene-bis triazol (For-- .mula 5) with S-aminobenzoic acid--(2azo-l)-- [1- (4' -sulfophenyl) -3-methyl-5-pyrazolonel.

When condensing the nitrostilbenebis-triazol (Formula 5) with the monoazo dyestufi from diazotised l-amino-Z-benzoic acid and 2-amino- 5-hydroxynaphthalene-7sulfonic acid, a brownred dyestuff will be obtained. The after-coppered dyeing possesses very good fastness properties to washing, water andto light.

Example 10 11 salts, are distinguished by a good washingan water-fastness.

A similar dyestufi is obtained by condensing the nitrostilbene-bis-triazol (Formula 12) with 5-aminobenzoic acid- (2-azo-4) [1- (4 -sulfophenyl) -3-methyl-5-pyrazolonel. If the nitrostilbenebis-triazol (Formula 12) is condensed with the monoazo dyestufi obtainable from diazotised 1- amino-2-benzoic acid and 2-amino-5-hydroxy naphthalene-'l-sulfonic acid, a dyestufi is obtained which dyes cellulosic fibres, when aftercoppered, in brown-red shades and possesses good fastness properties to light and in the moist state.

Example 11 40 parts of 4:4-nitroaminostilbene-2:2'-disu1- fonic acid are coupled with 38.5 parts of 5-amino- 2-(4'-hydroxy-3'-carboxy 5' sulfophenyl) 6 chloro-l:3-benztriazol and oxidised in the usual manner to the nitrostilbene-bis-triazol (Formula 13), 79.4 parts of the said nitrostilbene-bis-triazol are condensed at boiling temperature under reflux for 15-20 hours with 32.9 parts of the monoazo dyestuff obtainable from diazotised 1- amino-2-benzoic acid and 2-amino-5-hydroxynaphthalene-'l-sulfonic acid in 1600 parts of water and 400 parts of caustic soda lye of 36 B. Then the dyestufi is isolated. It is a brown powder dissolving in water with a reddish-brown coloration and dyeing cellulosic fibres in brown-red shades. By an after-treatment with copper salts the light-fastness and the fastness' properties in the moist state are considerably increased.

A yellow dyestufi having similarly good fastness properties in the moist state may be obtained by condensing the above described nitrostilbene-bis- 12 triazol (Formula 13) with S-aminobenzoic acid- (2-azo-4) -1-phenyl-3-methyl-5-pyrazolone.

Example 12 42 parts of 5-amino-2:2'(4:8-disu1fonaphthyl)-l:3-benztriazol are coupled with 40 parts of dia-zotised 4:4-nitroaminostilbene-disulfonic acid and the obtained dyestuff is oxidised to the nitrostilbene-bis-triazol in the manner described in Example 8. 80.8 parts of this nitrostilbenebis-triazol (Formula 11) are condensed as usual with 41.6 parts of 5-aminobenzoic acid-(Z-azo- 4) [1- (4' -su1fophenyl) -3-methyl-5 pyrazolone], the dyestufi being finally isolated. The same is a yellow-brown powder which dissolves in water with a yellow coloration and dyes cellulosic fibres in yellow shades. The fastness properties to washing and to Water may be improved by an after-treatment with copper salts. When coppering in substance according to any one of the known methods the metallised dyestuff is obtained in form of a brownish-yellow powder dissolving in water with a yellow coloration and dyeing cellulosic fibres in clear yellow shades of good fastness properties to washing and to water and of a very good light-fastness.

In the following table further combinations being possible according to the present invention will be enumerated; in each case the nitroand amino-components used for the condensation are indicated.

In connection with the above explanations it may be stated that the copper lakes can, of course, also be prepared in substance and not only on the fibre. In the former case partly very diflicultly soluble products will be obtained.

nitrostil- I fter treatbene-bisshade of the a t of the shade of the after- No. tnazol Amine or ammoazo dyestufl dyeing on met-1 compound of cellulose ggig gj treated dyemg the formula 1 No. 8 4-amino-2-methoxy-1:1-azobenzene-5-sulfonic acid orange-brown. red-brown.

d 4-am1n0-2-mcth0Xy-2-hydroxy-5-chloro-12l-azobenzene yellow-brown. brown 1-amino-2-hyclroxybenzene-E-sulfamide 2-amino-5-hybrown I D drqxynaphthalenefl-sulfonic acid l-ammo-5-chlorobenzene-2-carboxylic acid 2-amino-5- red-brown..." D0 hydroxynaphthalene-7-sulfonic acid l-ammo-4-acetylaminobenzene-2-carboxylic acid l-phenylyellow yellow.

3-methyl-5-pyrazolone saponified benzene zene-5-sullonic acid naphthalene naphthalene-7-sulfonic acid 3-methyl-pyrazolone, saponified acid 4 -amino -2 -methyl 5 -methoxy -4-hydroxy -3 zene-5-sulfonic acid naphthalene 1-am1no-4-acetylaminobenzene-Z-carboxylic l-aminonaphthalene-fi-sulionic acid r 1 4-amino-2-methyl-5-methoxy-4-hydroxy-3'- 1-ammo-4hydroxybenzene-3-carboxylic acid 4-amino-2-methoxy-4 -hydroxy-1 :1 -azobenzene-3 -carboxylic acid l-amino-2-hydroxybenzene-dsuliamide 4:4-a nino-acetyl-amino-diphenyl salicylicacid,saponifiedl-amino-4-acetyl-aminobenzene-Z-carboxylic acid 2-phenylamino-5-hydroxynaphthalene-7-sulfonic acid, saponified Lamino-4-acetyl-aminobenzene-Z-carboxylicacid l-phenyl- -amino-3-methylyellow-orange. yellow-orange.

o I carboxy-Ll -ezobenorange Flange l-aminobrown-red }brown-red.

brown-violet. red-orange-.." brown-red. 2-amino-5-hydroxyb }bmwn yellow. grey-violet.

yellow yellow.

yellowomnge }yelloworan gc. -carboxy 1.1 azoben orange }omnge do }orange.

redprange.

l-amino-4-acetyl-aminobenzene-2-carboxylicacid 2-pheny1- amino-5-hydroxy-naphthalene-7-sulfonic acid, saponified 4:4-ammo-acetylaminodiphenyl salicylic acid, saponifled.

I-amino-4-hydroxy-benzene-3-carboxylic acid 1 2-(4-aminopheny1)- (naphtha-1'12 :415-triazol)-5:7:gisulionic acid.

aci droxynaphthalene-3-carboxy1ic acid, saponifled brownish-red. brown-red.

yellow yellow. l-aminoorange-reinsbrown-orange.

violet-brown. yellow yellow.

-+ 2-hyreddish-brown brown.

l-amino-4-acetylaminobenzene-Z-carboxylic acid -o l-(4hyyellow Or grgxyW-carboxyphenfl)-5-pyrazolone-carboxylic acid-3, saponi- {Cu e 23 ..do 2-(4-aminophe11yl)-(naphtho-lzZ:4:5-triazol)-4-sulfonic acid d0 Do 24 do l-aminobenzene-z-carboxyllc acid --0 2-amino-5-hydroxybrownish-redred-brown.

naphthalene-7-sulfonic acid r 25 No.7 l-aminobenzene-Z-carboxylic acid. .v 2-amino-5-hydroxydo Do.

naphthalene-7-sulf0nic acid 26--- Nc;9 dehydrothio-p-toluidine-sulfonic acid yellow Or yellow. 27 do 1-ammo-4-acetylaminobenzene-2-carboxylic acid 1- do Ou Do.

phenyl-3-methyl-pyrazolone, saponlfled nitrostilbene-bisshade of the after treat No. triazol Amine or aminoazo dycstufi dyeing on mer-1t of Shade of the a compound of cellulose ig 'gi treated dyeing the formula a o 28. No. 9 l-amino-l-acetylaminobenzene-2-carboxylic acid 1-(4-hyyellow n droxy-3-carboxyphenyl)-3-metl1yl-5-pyrazolone, saponified ye 29 ..do l amino 4- acetylamlnobenzene 2- carboxy1ic acid 1 yellow-orange yellow-orange.

phenyl-pyrazolone-3 carboxylic acid, saponified 30-.... No. 10 l-aminoachlorobcnzene-z'carboxylic acid 2-amino-5-hybrown-red..... brown.

droxynaphthalene-7-sulfonic acid 31 do 1-aminobenzene-2-carboxylic acid 2'amino-5-hydroxybrownish-red" Cu red-brown.

naphthalenc-7-sulfonic acid l-amino-4-acetylaminobenzenc-2-carboxylic acid 1-(4-sulyellow Cu yellow.

iophenyl)-3-methyl pyrazolone, saponified dehydrothio-p-toluldine-sulionic acid 2-(4-aminophenyD-(naphtho-l: 2: 4: 5-triazoD-5: 7-disnlfonic acid.

4-amino-4-liydroxy-diphenylmcthanc-3-carboxylic acid }yellow do. 2-[5-l1ydroxy-Wsulfonaphthyl-(2)1-5-amino-benztriazol yellow-orange. {gm i }ye11 0 or ang e r No. 11..... 2-(4-hydroxy-3-carboxy-5-suliophenyl)-5-amino-l:3-benztriazol-.. do {8n D 0 No.13 i. l-amino-4-acetylaminobenzene-Z-carboxylic acid l-phenylyellow {Cu u S-methyl-fi-pyrazolone, saponified. (r ye 39..." No. 14...... l-amino4-acetylaminobenzenc-2-carboxylic acid l-(4-su1- ....do {Cu D fophenyl)-3-methyl-5-pyrazolone, saponified. Or

40 No. 15 l-amino+acetylaminobenzene-Z-carboxylic acid 1-(4-hyyellow-orange Cu firgxy-W-carboxyphenyl)-5-pyrazo1one-3-carboxylic acid, saponi- {Gr e 41. No. 16 1amino-4-acetylaminobcnzeue-2-carboxylic acid l-(3-caryellow {Cu enow boxyphenyl)-3-methyl-5-pyrazolone, saponified. Or y nitrostilbene-bisshade in triazol compound: amme 'chromesprinting formula No. 7 4-amino-4-hydroxy-3-carboxy-diphenyl-amine-2-sulfonic acid yellow-orange. formula No. 8. ..d0..... U Do. formula No. 7 4-amino-diphenyl-aminc-3:2-d1sulfon1c acid Do. ,do 2-(4-aminophe11yl)-(naphtl1o 1: 2: 4: 5-triaz01)-3t 6:.8-trisulionic acid Do.

What We claim is:

1. Process for the manufacture of stilbene dyestuffs comprising condensing, in a caustic alkaline medium at elevated temperature, an aromatic l S0311 S0311 wherein A means a member selected from the group consisting of benzene and naphthalene radicals containing at least one group imparting solubility in water, and X means a member selected from the group consisting of H, SOsI-I, COOH, halogen, alkyl and alkoXy.

2. Process for the manufacture of stilbene dyestufis comprising condensing, in a caustic alkaline medium at elevated temperature, an aminoazo dyestuif with a nitrostilbene-bis-tri- LZN CM M I 30311 SOaH (icon 0:

azol of the general formula 66 with a nitrostilbene-bis-triazol of the formula 00011 N soln HO N\ N/ \N S0311 S0311 MlQCnCHQNO,

16 4. Process for the manufacture of a stilbene V with a nitrostilbene-bis-triazol of the formula Hots N SOzH N- NOCH= -OHQNOz 7 11 0311 s 03H dyestufi comprising condensing, in a caustic al- 6. The stilbene dyestuffs obtained according to kaline medium at elevated temperature, an amithe process claimed in claim 1. noazo dyestuff of the formula 7 7. The stilbene dyestuffs obtained according to 15 the process claimed in claim 2. H2NON= 0H--ccm 8. The stilbene dyestufi obtained according to i 6 l; the process claimed in claim 3. COOH 9. The stilbene dyestufi obtained according to the process claimed in claim 4. 10. The stilbene dyestuff obtained according to the process claimed in claim 5.

ERNST KELLER.

SOQH V REINHARD ZWEIDLER.

with a 'nitrostilbene-bis-triazol of the formula 20011 /N\ V Q SOsH N/ N'N,QCH=CH NOz SOaH 8'03]: 5. Process for the manufacture of a stilbene REFERENCES CITED dyestufi comprising condensing, in a caustic alkanne medium at elevated temperature an The following references are of record in the noazo dyestufi of the formula 40 file of thls patent' UNITED STATES PATENTS H N N=NCH-(IT-CHs Number Name Date (IIOOH =C\ 2,029,591 schindhelm et a1. Feb. 4, 1936 a V N 2,056,539 Schindhelm et al Oct. 6, 1936 2,232,078 Schindhelm Feb. 18, 1941 2,248,151 Winkeler et al July 8, 1941 2,270,451 Keller Jan. 20, 1942 

